Method for removing metal halide vapors from a hydrocarbon reaction product



Oct. 14, 1947. C, o, MEYERS 2,428,981

METHOD FOR REMOVING METAL HALIDE VAPORS FROM A HYDROCARBON REACTION PRODUCT Filed March 20, 19.44

N-PARRAFm /HYDRocARBoNs HCL INVENTOR C. O. MEYERS AWQRZEYS2 Patented Oct. 14, 17947 METHOD VgFOR REMovING' -MEClA'Lf- HALIDE VAPos; `FROM-Ai` HYDROCARBON BEAU:

TION PRODUCT* o 'f charls 1o. Meyers; laftllviue, ok1a-asigrofte Phillips Petroleum-Company; acorporaton of" Delaware 4 Application Marclifzo, i944, SeriMNmmGs s Claims-WC1. 2,6() 3'83-5). 'l

This invention relates to a process for'the coni#4 Versionjotlow boiling 'hydroc'arbons'w'itl volatilizable `11iedel-'Cr'afts typmetl halide "catalysts" whereina stream'o'f the low'boilinghydrocarbons" f' is passednto contact Withsu'ch a "catalys't'urider is "hum haliderirem.-llrdrocarbon oiivereonfilu: .Y

'nis @Staining the-.Same- ...Anotber Qbieqt is. iol... Lffet the more complete, removal' Of Such metal. t halide iremuqh emi-rents: enoiherobieci .is to.A eff't SllhemQVl Within@ emllenillh, I3-100.. "phase Another object is to effect such removal .Without @Ketting thehrdrocarbqn pelli/.drogen 'halide `mientojf;theeefiluent being .treated-N111 x Yfmerousother objects will more fully hereinafter conditionsteifecting" the desired conversion'and" such thatsem'e of'sard metaljhaiide catalyst incorporated in the eiiluentL4 stream which) may' be either liquid or gaseous;`m' ore usually'thelat ter. More 1oarticularlyy 'it' relates 't`` process of l 0f the foregoing type'for 'the isomeriz'ation of norinal f parans to'isjoparaftlns'jby mea'ns of'a v la'tiliz`a""'`L ble aluminumlhalidefas acatalyst in the presence" of a hydrogen halide as a promoter arid whereinj f' nelu'en't is eommonlyjvap'orous "151m the isomerizatio althoughl itmayV be liquid in 'rare instances.`- The aluminum halide i's usually `aluminumv chloride" althoughaluminu'm bromide may less 'preferably be employed. Generallyfthe hydrogen halide cor'" respondsto thealuminumhalide and isalmost Pio invariably anhydrous.

The present invention relates to a method f'v" removing the volatilized Ametal Qhalide "catalyst from vaporous conversion effluents of the'1 )'rego v ing type, or of dissolved ymetal halide catalyst "'25 from liquid conversion eiuentsiofthe foregoing type in the relatively uncommon situation where -f the effluent is liquid.' The presence of volatiliza`v ble metalhalide in eliluen'ts' Of this typisvery undesirable-inasmuchas -it promotes' corrosion: "30' and erosion of the equipment, causes'pluggingo the equipment and numerous other difficulties."

Various schemes have beeniprop'osd inthe past for removal of'dissolved'or'volatilized catalysts but for a number'of reasons vnone of' them been commonly adopted'so far as I am aware.

In the' eopenuiiig 'applications' fnachmutn fi A and Baker, serian No. 460.702, nieu october` 3,'

1942, and of Hachmuth, Serial No. 460,703, led on the saine date,-no'w U; S. Patent No; 2,396;173,-"40" there is disclosed the idea of removing'volat-ilized f' aluminum chloride fromanisomerization eillu'ent by scrubbingwith aluminum nchloride"sludge which may be formed' by reaction of the aluminum chloride fwith an vunsaturated hydrocarbon* such as a liquid olenic polymer.

an improvement over the l'processes disclosed; in

My in In some aspectfsjv i the present inventionV may be considered' to be erablyf-i be had tiret fr a Iore detailed understanding 0f the bakgreurid; bf the. presepi iaveiltin- The Drincbalobiet @fthe Prsent ini/emblems 'to prQvideaLimprQi/.ed process @Hemi/ine a @utilizable .man1 .lialiderespeially 1a11. alumiappear.

tak' aiiferie..nigeriano? qlisiitit per Se any part'gf tlieqoresentinvention.

by a descri to the isonierizationtypical 7 application thereof other sludgelforihing [Inaterials` vwhich may b'e'ff' The acoirip'higf'drawine portrays. diagram-.1 Ofrfarangeieeiliof. equitinentwhich fifcarrying grit-the present ini/enr.. b liedersftod that the reactor mar rous hydrogen' 'chloride' vapor maybe passed into or oniyai miumihlpnde siudee'innie" bottoni" "section," nd then through'abed 'orbedso-ffalu" minum Chloride. "The initial cdntactof theiee'd the primaryI chamber :which [contains af'bed 'for beds ofaliir'ninumchloride. jIfdesi'r'ei fluids may"y be introduc "jat jai, multitude of l*pointsfin the 'streamqrf iii the ehambertqcontroi the tempera: ,ture and/orwtherreactin,"as isjdisclosed in'fthe 'opending*application of" HachIniuth, i Serial "No5 .The vapor then passes'through 'the'uppi' partjof f chambersfm'ay bepasseerv through a.V secondary" hamberfo "chamberscontainingfbauxite (prefthese cbpending^-applicatins -a'jnd-Areference"-y 565fPoroclifffffiillers earth orsome other Supporte" ing material, The treatment in the secondary chamber or chambers serves the dual purpose of removing sublimed aluminum chloride catalyst in the eilluent vapors and also increasing the conversion of straight chain hydrocarbons to branched chain hydrocarbons by the catalytic effect of the aluminum chloride catalyst removed from the eflluent. In fact, the extent or degree of conversion in the secondary chamber is often much greater than that `in the primary chamber so that it is often desirable to dispense with the primary chamber.

The effluent from the secondary chamber contains volatilized aluminum chloride as well as the normal paraln and isoparafn, the hydrogen chloride, and any hydrogen, light hydrocarbons, and heavier hydrocarbons formed in the isomerization. In accordance with the present invention, the aluminum chloride content thereof is removed therefrom in the following manner. This vaporous eilluent is passed directly into the bottom of a catalyst scrubber which is preferably vertical. The bottom of the catalyst scrubber contains an aluminum chloride complex olenic polymer sludge. A portion of the scrubber above this sludge is filled with Raschig rings or some other contacting material. It may be desirable to leave space above the packing material for any entrained liquid to settle out of the escaping vapors. An aluminum chloride complex olennc polymer sludge is continually pumped from the bottom of the scrubber into an intermediate point of the section of the tower which contains the Raschig rings so as to wet a complete crosssec tion of the Raschig rings and drain down over the rings countercurrently to the upward flow of vapors in the scrubber.

As the olenic polymer sludge becomes spent by absorbing or reacting with the sublimed aluminum chloride it is withdrawn from the catalyst scrubber and additional fresh olenic polymer is pumped into the scrubber at a point well above that at which the recirculated sludge is introduced. This fresh olenic polymer maintains the Raschig rings above the point of introduction of recycled sludge in a wetted condition so that the vapo-rs are given a nal scrubbing with fresh polymer whereby any traces of volatilized aluminum chloride are removed therefrom before they leave the scrubber. The fresh olenic polymer may be added at the top of or above the top of the Raschig rings and serves to trap or absorb orreact with any sublimed aluminum chloride which may be in the hydrocarbon vapors. The eiiluent from thecatalyst scrubber is completely free of aluminum chloride and may be passed directly to the conventional recovery system wherein there are separated a stream of recycle hydrogen chloride, a stream of product iso-parafns and a stream of recycled normal paraflins. If desired, the ellluent from the scrubber may rst be passed into a guard chamber filled with van absorbing agent such as bauxite or Porocel This guard chamber serves only as a safety measure. If something should go wrong with the operation of the catalyst scrubber and allow sublimed aluminum chloride vapors to pass out of the top with the hydrocarbon vapors, such a guard chamber would function to remove the aluminum chloride and keep it out of the remainder of the system.

Referring to the drawing, no-rmal paraflin feed enters via line I and, after admiXt-ure with a suitable proportion of hydrogen chloride or other hydrogen halide introduced by line 2, is passed into primary reactor 3. The eiluent from reactor 3 passes via line 4 into secondary reactor 5. The vaporous eilluent from chamber 5 passes via line 6 into the bottom of scrubber 'I. scrubber l is composed of two sections,y 8 and 9. Scrubber 'I further comprises a tray I0 which supports packing II of Raschig rings or the like, the packing extending over the major portion of the scrubber l. In the lower portion 8 of scrubber 1, the effluent vapors are scrubbed countercurrently with recycled aluminum chloride and polymer sludge which is introduced via line I2 and spider I3. The liquid sludge is withdrawn vla line I4 and recycled by means of pump I5 and line I2. A portion of the sludge is discarded as necessary via line I6 in order to prevent the sludge from accumulating to an excessive extent in scrubber l. The liquid level of the sludge is kept substantially below spider I3. Fresh liquid olenic polymer is continuously introrluced into the upper portion 9 of the scrubber I Aby means oi line I'I and spider I8. The scrubbed effluent free of aluminum chloride 0r other volatilizable metal halide, is withdrawn from the top via line I8 and, after passage through a guard chamber 20 if desired, is passed via line 2I t0 the recovery system.

It is preferred that the portion of sludge which is discarded be chemically equivalent in amount to the amount of fresh oleiinic polymer introduced at the top of the scrubber. In other words, the discarded sludge should contain in chemically combined form or otherwise, an amount of olefinic polymer substantially equal to that continuously being introduced by line I'I.

It is preferred that the scrubbing with fresh polymer should be so carried out that all traces of metal halide are removed from the effluent. Often, it is preferred that the length of the scrubbing tower between tray I0 and spider I3 be equal to the length between spider I3 and spider I8 or the top of packing II so that the fresh olefinic polymer intimately contacts the vaporous efuent for a period of time approximately equal to that for which the recycled sludge contacts the eluent.

It will be understood of course that as the fresh olefnic polymer descends in section 9, it is at least partially converted to sludge and joins with the recycled sludge introduced via line I2, being used in conjunction therewith in sectionV 8 for the initial scrubbing.

Example 1000 barrels per day of a hydrocarbon feed consisting essentially of normal butane and 5% hydrogen chloride by volume were contacted with aluminum chloride to produce isobutane. The reaction was carried out in a reactor in which the pressure was p. s. i. and the temperature 200 F. The eiiluent from the reactor passed through a secondary chamber which contained Porocel and wherein most of the aluminum chloride contained in the vapors was deposited on the PoroceL The vaporous effluent from the secondary chamber passed into a scrubber which was a tower 4 ft. in diameter and 30 ft. high. There was a tray 21/2 ft. from the bottom of the tower on which Raschig rings were supported. The Raschie rings filled the portion of the tower above the tray. A. liquid levelV of 6 ft. was maintained in the tower. This liquid was recirculated at a rate of 20 gal. per hour into a spider which was located' 15 ft. from the bottom of the chamber. 21/2 gal. per hour of olenic polymer of approximately 0.8

specific gravity was fed into the tower at a point 25 ft. from the bottom ofthe scrubber. The entering butane-hydrogen chloride feed to the scrubber contained 0.1% aluminum chloride vapors by weight of hydrocarbons. The recycled uid contained 23.0% aluminum chloride. The vaporous eiiiuent leaving the scrubber was at a pressure of 165 p. s. i. and was free of aluminum chloride.

The present invention presents a number of advantages over prior art practice. Among these is the fact that every trace of metal halide is removed from the elluent being scrubbed. Another advantage is that the scrubbing liquid resulting from the nal scrubbing with fresh polymer commingles with the recycled sludge and is ultimately recycled "along" therewith. Still another advantage is that the'maj'or portion of the metal halide is removed in the initial scrubbing with reciroulated sludge. Numerous other advantages will be apparent to those skilled in the art,

The term aluminum chloride complex oleinic polymer sludge as used in this specification refers to a pumpable liquid sludge which is formed by incorporating a minor amount of aluminum chloride in an olefin polymer, some unsaturated linkages being present in the polymeric material. The term is used to distinguish this relatively inactive material from the active aluminum chloride-hydrocarbon complex catalysts widely used in alkylation and isomerization processes.

I claim:

1. In a process for conversion of low-boiling hydrocarbon with a volatilizable Friedel-Crafts type metal halide catalyst which comprises passing a stream of low-boiling hydrocarbon in contact with such a catalyst under conditions effecting the desired conversion and such that some of said metal halide catalyst becomes incorporated in the effluent stream` the improvement which comprises removing said metal halide from said effluent stream by intimately countercurrently contacting same in vapor phase in a rst scrubbing zone with metal halide complex clenic polymer sludge withdrawn from the bottom of said zone and re-intro-duced thereto and thereby causing the major part of said metal halide to be absorbed from said effluent stream by said sludge, then intimately countercurrently contacting the resulting eiluent stream in vapor phase in a second scrubbing zone with fresh liquid olefinic polymer and thereby causing the remainder of said metal halide to be absorbed from said effluent stream by reaction with said fresh polymer, withdrawing the treated efuent stream free from metal halide from said second zone, and withdrawing from said second zone the resulting olefinic polymer and introducing same to said first Zone and employing same therein in conjunction with said recirculatecl sludge for the first scrubhing step. V

2. In the isomerization of normal paraiiins to isoparaims by means of a volatizable aluminum halide as a catalyst in the presence of a hydrogen halide as a promoter and wherein the isomerization eiiiuent is vaporous and contains volatilized aluminum halide, the method of removing said volatilized aluminum halide from said vaporous eliiuent which comprises continuously introducing said eiiluent into a low point of a vertical scrubbing zone and passing same upwardly therein in intimate countercurrent contact rst with aluminum halide complex oleinic polymer sludge withdrawn from the bottom of said zone and continuously introduced into an intermediate point of said zone and then with 6. fresh olefnic polymer continuously introduced at' a hi'ghipoint `of said zone, continuously withdrawing aluminum halide complex olefinie polymer sludge. from the bottom of said zone and introducing same continuously into said zone at an intermediate point thereof, continuously introducing fresh liquid olenic polymer into said zone at a high point therein, and continuously withdrawing treated vaporous eiiluent free from aluminum chloride from the top of said zone.

3. The process of claim 2 wherein a portion of said withdrawn sludge is discarded from the sys temin amount chemically equivalent to that of said fresh olenic polymer introduced into said zone.

4. 'In the isomerization of normal butane to isobutane by means of aluminum chloride as a catalyst in the presence of hydrogen chloride as a promoter and wherein the isomerization eilluent is vaporous and contains volatilized aluminum chloride, the method of removing said volatilized aluminum chloride from said vaporous efliuent which comprises continuously introducing said efuent into a low point of a vertical scrubbing zone and passing same upwardly therein in intimate countercurrent contact rst with aluminum chloride complex olenic polymer sludge withdrawn from the bottom cf said zone and continuously introduced into an intermediate point of said Zone and then with fresh olefinic polymer continuously introduced at a high point of said zone, continuously withdrawing aluminum chloride complex oleflnic polymer sludge from the bottom of said zone and introducing same continuously into said zone at an intermediate point thereof, continuously introducing fresh liquid oleiinic polymer into said zone at a high point therein, and continuously withdrawing treated vaporous eiiiuent free from aluminum chloride from the top of said zone.

5. The process of claim 4 wherein a portion of said withdrawn sludge is discarded from the system in amount chemically equivalent to that of said fresh clenie polymer introduced into said zone.

6. The process of claim 4 wherein said intermediate point is substantially the mid-point of said zone and wherein said fresh oleiinic polymer contacts said vaporous effluent for a period of time equivalent to that for which the recirculated sludge contacts said efiiuent.

7. The process of claim 1 wherein a portion of the sludge withdrawn from the first Zone is discarded from the system in amount chemically equivalent to the amount of fresh polymer introduced to the second zone whereby the sludge is kept from building up in the iirst zone.

8. The process of isomerizing normal butane to isobutane which comprises contacting a hydrocarbon feed consisting essentially of normal butane and 5 per cent hydrogen chloride by volume with aluminum chloride under conditions such as to effect isomerization of said normal butane to isobutane, passing the vaporous effluent through a secondary chamber to remove most of the aluminum chloride therefrom, passing the resulting vapors containing 0.1 per cent aluminum chloride by Weight of hydrocarbons into the bottom of a packed vertical tower and countercurrently contacting same with recirculated aluminum chloride complex olenic polymer sludge containing 23.0 per cent aluminum chloride, withdrawing said sludge from the bottom ,of said tower and re-introducing it into the mid-point thereof at the rate of 20 gallons per hou'r per 1000 barrels lper day of said feed, con-y tinuously introducing fresh olenic polymer into the top of said tower at the rate of 21/2 gallons per hour per 1000 barrels per day of said feed and causing the vapors after they have traversed the bottom half of said tower to countercurrently.

contact said fresh olenic polymer in the upper half of said tower, withdrawing the resulting Vaporous eiliuent free of aluminum chloride from the top of said tower, and discarding a portion of the sludge withdrawn from the'bottom of said tower from the system in amount chemically equivalent to the amount of said fresh polymer introduced into the top of said tower.

lCHARLES o. MEYERS.

'REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 1,578,049 McAfee Mar. 23, 1926 2,003,235 Bennett May 28, 1935 2,317,241 Ackerman et al Apr. 20, 1943 2,356,190 Voorhies Aug. 22, 1944 2,342,123 Danforth Feb. 22, 1944 2,304,290 Van Peski DeC. 8, 1942 2,378,773 Sensei June 19, 1945 2.395.022 Sutton et al Feb. 19, 1946 2,314,297 Watson Mar. 16, 1943 2,281,924 deSimo et a1 May 5, 1942 Certcate of Correction n Patent No. 2,428,981. October 14, 1947. CHARLES O. MEYERS It is hereby certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Column 5, line 62, claim 2, for volatizable read volotil'izable; column 8, line 13, list of references cited, for the number 2,37 8,773, read 2,378,733; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oiiice.

Signed and sealed this 20th day of January, A. D. 1948.

THOMAS F. MURPHY,

Assistant Oamnnsszoner of Patents. 

